US20040097388A1 - Highly polar cleans for removal of residues from semiconductor structures - Google Patents
Highly polar cleans for removal of residues from semiconductor structures Download PDFInfo
- Publication number
- US20040097388A1 US20040097388A1 US10/454,109 US45410903A US2004097388A1 US 20040097388 A1 US20040097388 A1 US 20040097388A1 US 45410903 A US45410903 A US 45410903A US 2004097388 A1 US2004097388 A1 US 2004097388A1
- Authority
- US
- United States
- Prior art keywords
- carbon dioxide
- supercritical carbon
- ionic liquid
- residues
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004065 semiconductor Substances 0.000 title description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 41
- 239000002608 ionic liquid Substances 0.000 claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- -1 imidazolium compound Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000006184 cosolvent Substances 0.000 claims 2
- 125000001153 fluoro group Chemical group F* 0.000 claims 2
- 239000011538 cleaning material Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 4
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001020 plasma etching Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Definitions
- This invention relates generally to processes for manufacturing semiconductor integrated circuits and, particularly, to the removal of etch residues.
- Fluorine-based plasma etching is commonly used to etch photoresist to generate patterns on a semiconductor device.
- a residue is left behind on the etched wafer that essentially includes constituents of the plasma gas and the material etched. Normally, gases composed of carbon and fluorine are used for plasma etching resulting in a residue containing carbon and fluorine. Further, the residue may be polymerized due to the generation of free radicals and ions in the high-energy plasma environment.
- etch residue may be difficult to remove.
- This residue may include carbon, hydrogen, and fluorine, and is highly chemically inert and is, therefore, relatively difficult to remove with conventional wet chemical etches.
- the use of delicate interlayer dielectrics, including porous materials, may prevent the use of ashing for residue removal. Conventional wet cleans may not work well with this relatively inert chemical residue. Few liquid solvents can penetrate fluorine-based polymers like teflon.
- Supercritical carbon dioxide has gas-like diffusivity and viscosity and liquid-like densities, while being almost chemically inert. Hence a host of chemically reactive agents may almost always be used in conjunction during supercritical carbon dioxide-based cleans. Carbon dioxide becomes supercritical at temperatures above 30° C. and pressures above 1000 pounds per square inch. A fluid is considered to be supercritical when its pressure and temperature are above the critical values.
- a variety of chemically reactive agents are soluble in supercritical carbon dioxide, such as the solvents dimethyl acetamide (DMAC), sulfolane, organic peroxides, ethers, glycols, organic bases, and strong organic and mineral acids, to mention a few examples.
- DMAC dimethyl acetamide
- sulfolane organic peroxides
- ethers organic peroxides
- glycols organic bases
- strong organic and mineral acids to mention a few examples.
- the higher degree of swelling of the fluorine-based residue by fluorocarbons dissolved in supercritical carbon dioxide and increased diffusion of supercritical carbon dioxide and the dissolved reagents therein (fluorocarbons and the other chemical reagents) may enhance residue deterioration and removal.
- a high flow rate of supercritical carbon dioxide may lend the ability to use highly reactive chemicals as opposed to conventional wet chemistries, which have a long contact time with the dielectric material.
- Ionic liquids are salts that exist in liquid form at temperatures from 10 to 200° C. Ionic liquids have a positive and negative charge. They exhibit low viscosity and no measurable vapor pressure. Ionic liquid can dissolve a range of organic, inorganic, and polymeric materials at high concentrations. Generally, ionic liquids are non-corrosive. Examples of ionic liquids include salts of alkylmethylimidazolium.
- a member from the imidazolium family of ionic liquids may be combined with supercritical carbon dioxide to increase variability and polarity and hence selectivity for various cleaning applications.
- the ionic liquid may be mixed into supercritical carbon dioxide in a way that the ionic liquid is fully, or only partially, miscible in the carbon dioxide medium, depending on the application.
- Supercritical carbon dioxide may be forced through a solution containing the undesired material and an ionic liquid.
- the carbon dioxide in its supercritical state may be near room temperature but is highly pressurized.
- the supercritical carbon dioxide may have a liquid consistency yet, like a gas, expands to fill the available space.
- droplets of supercritical carbon dioxide are forced through an ionic liquid, the carbon dioxide can pull impurities out of the ionic liquid while leaving the ionic liquid unchanged.
- Carbon dioxide is sufficiently soluble in 1-butyl-3-methylimidazolium hexafluorophosphate to reach a mole fraction of 0.6 at 8 MPa. Blanchard, Lynette A. et al., Nature, 399, 28-29 (1999).
- Dissolved fluorocarbons or other reagents in supercritical carbon dioxide may be quickly transported into residues left after fluorine-based etches of photoresist due to the high diffusivity of supercritical carbon dioxide and, particularly, the diffusivity of supercritical carbon dioxide in polymers and small molecules in polymers swollen by supercritical carbon dioxide. Since the fluorocarbons are chemically similar to the etch residue, the etch residue swells. This further increases the access of the supercritical carbon dioxide into the interior of the etch-residue and weakens the residue. The fluorocarbon also breaks into the hard crust of the residue, which the supercritical carbon dioxide by itself may be unable to enter and swell, to introduce the reactive agents into the residue. Addition of an ionic liquid to the above supercritical carbon dioxide/fluorocarbon mixture allows for polar variability/tunibility of said mixture.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Detergent Compositions (AREA)
Abstract
Supercritical carbon dioxide may be utilized to remove resistant residues such as those residues left when etching dielectrics in fluorine-based plasma gases. The supercritical carbon dioxide may include an ionic liquid in one embodiment.
Description
- This invention relates generally to processes for manufacturing semiconductor integrated circuits and, particularly, to the removal of etch residues.
- Fluorine-based plasma etching is commonly used to etch photoresist to generate patterns on a semiconductor device. A residue is left behind on the etched wafer that essentially includes constituents of the plasma gas and the material etched. Normally, gases composed of carbon and fluorine are used for plasma etching resulting in a residue containing carbon and fluorine. Further, the residue may be polymerized due to the generation of free radicals and ions in the high-energy plasma environment.
- With photoresists in advanced semiconductor processes, such as the 193 nm photoresist, wherein a fluorine-rich plasma etch is used, and with 157 nm, wherein the photoresist itself is fluorine-based the etch residue may be difficult to remove. This residue may include carbon, hydrogen, and fluorine, and is highly chemically inert and is, therefore, relatively difficult to remove with conventional wet chemical etches. The use of delicate interlayer dielectrics, including porous materials, may prevent the use of ashing for residue removal. Conventional wet cleans may not work well with this relatively inert chemical residue. Few liquid solvents can penetrate fluorine-based polymers like teflon.
- Thus, there is a need for a better way to remove resistant etch residues.
- Supercritical carbon dioxide has gas-like diffusivity and viscosity and liquid-like densities, while being almost chemically inert. Hence a host of chemically reactive agents may almost always be used in conjunction during supercritical carbon dioxide-based cleans. Carbon dioxide becomes supercritical at temperatures above 30° C. and pressures above 1000 pounds per square inch. A fluid is considered to be supercritical when its pressure and temperature are above the critical values.
- A variety of chemically reactive agents are soluble in supercritical carbon dioxide, such as the solvents dimethyl acetamide (DMAC), sulfolane, organic peroxides, ethers, glycols, organic bases, and strong organic and mineral acids, to mention a few examples. The higher degree of swelling of the fluorine-based residue by fluorocarbons dissolved in supercritical carbon dioxide and increased diffusion of supercritical carbon dioxide and the dissolved reagents therein (fluorocarbons and the other chemical reagents) may enhance residue deterioration and removal. A high flow rate of supercritical carbon dioxide may lend the ability to use highly reactive chemicals as opposed to conventional wet chemistries, which have a long contact time with the dielectric material.
- Ionic liquids are salts that exist in liquid form at temperatures from 10 to 200° C. Ionic liquids have a positive and negative charge. They exhibit low viscosity and no measurable vapor pressure. Ionic liquid can dissolve a range of organic, inorganic, and polymeric materials at high concentrations. Generally, ionic liquids are non-corrosive. Examples of ionic liquids include salts of alkylmethylimidazolium.
- A member from the imidazolium family of ionic liquids may be combined with supercritical carbon dioxide to increase variability and polarity and hence selectivity for various cleaning applications. The ionic liquid may be mixed into supercritical carbon dioxide in a way that the ionic liquid is fully, or only partially, miscible in the carbon dioxide medium, depending on the application.
- By mixing ionic liquids with supercritical carbon dioxide, clean chemistries with high polar variability may be achieved. For example, derivatives of 1-butyl-3-methylimidazolium hexafluorophosphate may be used which are partially miscible with supercritical carbon dioxide.
- The addition of highly polar ionic liquids in various stoichiometries to supercritical carbon dioxide provides a broader range of tunable polarities, enabling variation and selectivity for material cleaning. Moreover, such liquids have effectively zero vapor pressure and, therefore, they can be recycled upon heating. The particles and solutes are degraded and then can be filtered or separated off. In addition, other ionic liquids may also be used with supercritical carbon dioxide. One may pick and choose among the various available ionic pairs to make a liquid that fits a particular need such as dissolving certain chemicals in a reaction or extracting specific molecules from solution.
- Supercritical carbon dioxide may be forced through a solution containing the undesired material and an ionic liquid. The carbon dioxide in its supercritical state may be near room temperature but is highly pressurized. The supercritical carbon dioxide may have a liquid consistency yet, like a gas, expands to fill the available space. When droplets of supercritical carbon dioxide are forced through an ionic liquid, the carbon dioxide can pull impurities out of the ionic liquid while leaving the ionic liquid unchanged. Carbon dioxide is sufficiently soluble in 1-butyl-3-methylimidazolium hexafluorophosphate to reach a mole fraction of 0.6 at 8 MPa. Blanchard, Lynette A. et al., Nature, 399, 28-29 (1999).
- Dissolved fluorocarbons or other reagents in supercritical carbon dioxide may be quickly transported into residues left after fluorine-based etches of photoresist due to the high diffusivity of supercritical carbon dioxide and, particularly, the diffusivity of supercritical carbon dioxide in polymers and small molecules in polymers swollen by supercritical carbon dioxide. Since the fluorocarbons are chemically similar to the etch residue, the etch residue swells. This further increases the access of the supercritical carbon dioxide into the interior of the etch-residue and weakens the residue. The fluorocarbon also breaks into the hard crust of the residue, which the supercritical carbon dioxide by itself may be unable to enter and swell, to introduce the reactive agents into the residue. Addition of an ionic liquid to the above supercritical carbon dioxide/fluorocarbon mixture allows for polar variability/tunibility of said mixture.
- While the present invention has been described with respect to a limited number of embodiments, those skilled in the art will appreciate numerous modifications and variations therefrom. It is intended that the appended claims cover all such modifications and variations as fall within the true spirit and scope of this present invention.
Claims (17)
1. A method of cleaning etch residues comprising:
exposing said etch residue to flowing supercritical carbon dioxide and an ionic liquid.
2. The method of claim 1 including exposing said etch residue to an ionic liquid including a fully, or a partially, miscible imidazolium compound.
3. The method of claim 2 including exposing said etch residue to 1-butyl-3-methylimidazolium hexafluorophosphate in supercritical carbon dioxide.
4. The method of claim 1 including providing a solvent with said carbon dioxide and ionic liquid.
5. The method of claim 4 wherein said solvent includes fluorine substituents.
6. The method of claim 1 including providing an ionic liquid which is only partially miscible in supercritical carbon dioxide and combining said ionic liquid and said flowing supercritical carbon dioxide.
7. The method of claim 1 including providing an ionic liquid which is fully miscible in supercritical carbon dioxide and combining said ionic liquid and said flowing supercritical carbon dioxide.
8. A cleaning material comprising:
supercritical carbon dioxide; and
an ionic liquid.
9. The material of claim 8 wherein said ionic liquid is only partially miscible in supercritical carbon dioxide.
10. The material of claim 8 wherein said ionic liquid is fully miscible in supercritical carbon dioxide.
11. The material of claims 9 or 10 wherein said ionic liquid includes an imidazolium compound.
12. The material of claim 11 wherein said compound is 1-butyl-3-methylimidazolium hexafluorophosphate.
13. The material of claims 9 or 10 including a co-solvent.
14. The material of claim 13 wherein said co-solvent includes fluorine substituents.
15. A method of removing etch residues comprising:
forming a mixture of 1-butyl-3-methylimidazolium hexafluorophosphate and supercritical carbon dioxide; and
flowing said mixture over said etch residue.
16. The method of claim 15 including forming a mixture in which the 1-butyl-3-methylimidazolium hexafluorophosphate is only partially miscible in supercritical carbon dioxide.
17. The method of claim 15 including forming the mixture with a solvent including a fluorine-based solvent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/454,109 US7022655B2 (en) | 2002-11-15 | 2003-06-04 | Highly polar cleans for removal of residues from semiconductor structures |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/295,150 US6624127B1 (en) | 2002-11-15 | 2002-11-15 | Highly polar cleans for removal of residues from semiconductor structures |
US10/454,109 US7022655B2 (en) | 2002-11-15 | 2003-06-04 | Highly polar cleans for removal of residues from semiconductor structures |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/295,150 Division US6624127B1 (en) | 2002-11-15 | 2002-11-15 | Highly polar cleans for removal of residues from semiconductor structures |
Publications (2)
Publication Number | Publication Date |
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US20040097388A1 true US20040097388A1 (en) | 2004-05-20 |
US7022655B2 US7022655B2 (en) | 2006-04-04 |
Family
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Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US10/295,150 Expired - Fee Related US6624127B1 (en) | 2002-11-15 | 2002-11-15 | Highly polar cleans for removal of residues from semiconductor structures |
US10/454,109 Expired - Fee Related US7022655B2 (en) | 2002-11-15 | 2003-06-04 | Highly polar cleans for removal of residues from semiconductor structures |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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US10/295,150 Expired - Fee Related US6624127B1 (en) | 2002-11-15 | 2002-11-15 | Highly polar cleans for removal of residues from semiconductor structures |
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US (2) | US6624127B1 (en) |
Cited By (30)
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US20060065627A1 (en) * | 2004-09-29 | 2006-03-30 | James Clarke | Processing electronic devices using a combination of supercritical fluid and sonic energy |
US7022655B2 (en) * | 2002-11-15 | 2006-04-04 | Intel Corporation | Highly polar cleans for removal of residues from semiconductor structures |
WO2006137957A1 (en) * | 2005-06-13 | 2006-12-28 | Gurin Michael H | Nano-ionic liquids and methods of use |
CN103351952A (en) * | 2013-06-05 | 2013-10-16 | 温州大学 | Extraction method of magnolia sieboldii plant volatile oil |
US8613195B2 (en) | 2009-09-17 | 2013-12-24 | Echogen Power Systems, Llc | Heat engine and heat to electricity systems and methods with working fluid mass management control |
US8616323B1 (en) | 2009-03-11 | 2013-12-31 | Echogen Power Systems | Hybrid power systems |
US8616001B2 (en) | 2010-11-29 | 2013-12-31 | Echogen Power Systems, Llc | Driven starter pump and start sequence |
US8783034B2 (en) | 2011-11-07 | 2014-07-22 | Echogen Power Systems, Llc | Hot day cycle |
US8794002B2 (en) | 2009-09-17 | 2014-08-05 | Echogen Power Systems | Thermal energy conversion method |
US8813497B2 (en) | 2009-09-17 | 2014-08-26 | Echogen Power Systems, Llc | Automated mass management control |
US8857186B2 (en) | 2010-11-29 | 2014-10-14 | Echogen Power Systems, L.L.C. | Heat engine cycles for high ambient conditions |
US8869531B2 (en) | 2009-09-17 | 2014-10-28 | Echogen Power Systems, Llc | Heat engines with cascade cycles |
US9014791B2 (en) | 2009-04-17 | 2015-04-21 | Echogen Power Systems, Llc | System and method for managing thermal issues in gas turbine engines |
US9062898B2 (en) | 2011-10-03 | 2015-06-23 | Echogen Power Systems, Llc | Carbon dioxide refrigeration cycle |
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US11988965B2 (en) | 2020-01-15 | 2024-05-21 | Lam Research Corporation | Underlayer for photoresist adhesion and dose reduction |
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US7553803B2 (en) * | 2004-03-01 | 2009-06-30 | Advanced Technology Materials, Inc. | Enhancement of silicon-containing particulate material removal using supercritical fluid-based compositions |
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- 2002-11-15 US US10/295,150 patent/US6624127B1/en not_active Expired - Fee Related
-
2003
- 2003-06-04 US US10/454,109 patent/US7022655B2/en not_active Expired - Fee Related
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